2,4'-dicyanodiphenylacetylene | 196080-60-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2,4'-dicyanodiphenylacetylene
• 英文别名: 2-(2-(4-(cyano)phenyl)ethynyl)benzonitrile；2-[2-(4-Cyanophenyl)ethynyl]benzonitrile
• CAS: 196080-60-1
• 化学式: C₁₆H₈N₂
• 分子量: 228.253
• InChiKey: HRDHLVYXYOUHRL-UHFFFAOYSA-N

物化性质

• 熔点：
  132-133 °C
• 沸点：
  450.2±30.0 °C(Predicted)
• 密度：
  1.22±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  47.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  三正丁基氢锡 、 2,4'-dicyanodiphenylacetylene 在 bis-triphenylphosphine-palladium(II) chloride 作用下， 以 甲苯 为溶剂， 以82%的产率得到
  参考文献：
  名称：

  Can Polarization of Triple Bond in Tolanes Be Deduced from ¹³C NMR Shifts? Re-evaluation of Factors Affecting Regiochemistry of the Palladium-Catalyzed Hydrostannation of Alkynes

  摘要：

  Polarization of the triple bond in a series of differently substituted ortho- and para-tolanes has been studied by NMR and computational methods in order to examine if C-13 NMR data can be effectively used for the assessment of electronic polarization of a triple bond in diarylacetylenes. DFT calculations of both natural charges and NMR properties revealed that chemical shifts concur with effective charges on sp-carbon atoms in para-tolanes, whereas in ortho-analogues magnetic anisotropy complicates the analysis making C-13 NMR data inapplicable for ascribing triple bond polarization. The obtained information was used to reevaluate factors affecting the regiochemistry of the Pd-catalyzed hydrostannation of the triple bond in tolanes. Computational study on the polarization of triple bonds taken together with the experimental data on hydrostannation of various mono- and disubstituted tolanes bearing para- and ortho-substituents demonstrated that the regioselectivity of hydrostannation is governed by a combination of electronic and steric factors. In para-tolanes, the electronic effect prevails and alpha- and beta-vinylstannanes are obtained predominantly for substrates with electron-withdrawing and electron-donating groups, respectively. In the ortho-series, steric factors dominate over electronics and a-isomers are produced with high selectivity regardless of the substituents' nature. However, it was found that in disubstituted "push-pull" tolanes steric control of an ortho-group can be overruled by the very strong electronic effect of an electron-withdrawing substituent in para-position.

  DOI：

  10.1021/ja051274v
• 作为产物：
  描述：

  2-溴苯腈 在 bis-triphenylphosphine-palladium(II) chloride 氢氧化钾 、 copper(l) iodide 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 氯仿 、 水 为溶剂， 反应 13.5h， 生成 2,4'-dicyanodiphenylacetylene
  参考文献：
  名称：

  具有杆状多氰基pi共轭结构的新型荧光团：合成和光物理性质。

  摘要：

  [反应：见正文]通过Pd交叉偶联反应合成了新型棒状聚氰基-低聚（亚苯基乙炔基）。发现多氰基基团极大地提高了OPE的发射效率（Phi（f））。通过最终的供体修饰，我们实现了具有SMe基团（Phi（f）= 0.972，对数epsilon 4.89，λ（em）455 nm）的非常强的蓝色发光荧光团的创建，以及NMe（2）组（Phi（f）= 0.999，log epsilon 4.75，lambda（em）555 nm）。还发现6和7的Phi（f）溶剂依赖性相反，并且在整个sigma（p）-X区域中，Phi（f）和sigma（p）-X之间存在线性关系。

  DOI：

  10.1021/ol0528991

文献信息

• Click-Reagent Version of Sonogashira Coupling Protocol to Conjugated Fluorescent Alkynes with No or Reduced Homocoupling
  作者：Subhendu Sekhar Bag、Rajen Kundu、Manas Das

  DOI：10.1021/jo200005n

  日期：2011.4.1

  A click-reagent version of the Sonogashira-coupling protocol has been developed. Diarylalkynes with donor and/or acceptor substituents have been synthesized via this protocol at moderate to excellent yields and with no or drastically reduced quantities of undesired homocoupled side products. This protocol is green-solvent compatible, air-insensitive, and effective under microwave conditions.
• Association of Dicyanodiphenylacetylenes with Silver(I) Salts in Solution and Solid State:  Electrospray Ionization Mass Spectrometry Samples Aggregates at Subsaturated Concentrations
  作者：Keith A. Hirsch、Scott R. Wilson、Jeffrey S. Moore

  DOI：10.1021/ja971135g

  日期：1997.10.1

  Complexes of 2,3'-dicyanodiphenylacetylene (2,3'-DCPA, 1), 2,2'-dicyanodiphenylacetylene (2,2'-DCPA, 2), and 2,4'-dicyanodiphenylacetylene (2,4'-DCPA, 3) with silver(I) salts have been characterized in the solid state by single-crystal X-ray analysis. In addition, aggregates of compounds 1-3 and silver(I) ions have been identified in solution by electrospray ionization mass spectrometry (ESI-MS). The topology of the structures in the solid state, namely finite versus infinite, is found to depend on the substitution pattern of nitrile groups on diphenylacetylene. For 2,3'-DCPA. (1), crystallization with silver(I) triflate (AgCF3SO3), silver(I) perchlorate hydrate (AgClO4 . xH(2)O, x similar to 1), or silver(I) hexafluoroantimonate (AgSbF6) produces cyclic dimers of composition [Ag(1)(X)](2) (X = CF3SO3-(4) or ClO4- (5)) and [Ag(1)](SbF6)}(2) (6). For these structures, 2,3'-DCPA coordinates to silver(I) ions in a cisoid conformation with respect to the orientation of nitrile groups. Significant deformations of the cyclic dimers are observed as a function of the counterion employed. In contrast to the finite structures involving 2,3'-DCPA, crystallization of 2,2'-DCPA (2) with AgCF3SO3 yields the infinite chain structure [Ag(2)(CF3SO3)] (7). 2,2'-DCPA coordinates to silver(I) in a transoid conformation resulting in a ''half-bow-tie'' motif for the chains. Crystallization of 2,4'-DCPA (3) with AgCF3SO3 produces the infinite, undulating sheet structure [Ag(3)(CF3SO3)] (8) in which helical chains of 2,4'-DCPA coordinated to silver(I) ions are bridged by triflate counterions. Positive ion ESI-MS of solutions of 2,3'-DCPA (1) and AgCF3SO3, AgClO4 . H2O, or AgSbF6 in acetone or acetonitrile show a distribution of aggregates including [Ag-2(1)(2)(X)](+) (X = CF3SO3-, ClO4-, or SbF6-). The composition of these species corresponds to that of the cyclic dimers of complexes 4-6 minus one counterion, X. With 2,2'-DCPA (2) and AgCF3SO3 in acetone or acetonitrile, the aggregates [Ag(2)](+) and [Ag(2)(2)](+) are observed and higher adducts are noted to be present in much lower abundance. It is believed that the predominance of adducts involving one silver(I) ion is due to the formation of chelated species in solution in which 2,2'-DCPA coordinates to a silver(I) ion in a cisoid conformation. Molecular modeling suggests that such species are viable. ESI-MS of 2,4'-DCPA (3) and AgCF3SO3 in acetone or acetonitrile shows the existence of [Ag(3)](+) as well as higher aggregates which are less prevalent. For a given Ligand, aggregation at concentrations of the Ligand and silver(I) salt of ca. 10(-3) M is significant in acetone, however, it is largely disrupted in acetonitrile due to the predominance of acetonitrile Ag(I) adducts. Analysis of the ESI-MS data for all three ligands with AgCF3SO3 in acetone or acetonitrile shows that the aggregate [Ag-2(L)(2)(CF3SO3)](+) is most abundant for L = 2,3'-DCPA (1). It is postulated that the relatively high abundance of [Ag-2(1)(2)(CF3SO3)](+) is indicative of the formation of a cyclic dimer in solution that resembles complex 4.Similarly, it is believed that cyclic dimers exist in solution with ClO4- and SbF6- as well.
• New Fluorophores with Rod-Shaped Polycyano π-Conjugated Structures:  Synthesis and Photophysical Properties
  作者：Yoshihiro Yamaguchi、Takanori Ochi、Tateaki Wakamiya、Yoshio Matsubara、Zen-ichi Yoshida

  DOI：10.1021/ol0528991

  日期：2006.2.1

  the emission efficiency (Phi(f)) of OPEs. By the end donor modification, we achieved the creation of very intense blue light-emitting fluorophore with the SMe group (Phi(f) = 0.972, log epsilon 4.89, lambda(em) 455 nm) and very intense yellow light-emitting fluorophore with the NMe(2) group (Phi(f) = 0.999, log epsilon 4.75, lambda(em) 555 nm). Contrasting Phi(f) solvent dependency of 6 and 7 and a linear

  [反应：见正文]通过Pd交叉偶联反应合成了新型棒状聚氰基-低聚（亚苯基乙炔基）。发现多氰基基团极大地提高了OPE的发射效率（Phi（f））。通过最终的供体修饰，我们实现了具有SMe基团（Phi（f）= 0.972，对数epsilon 4.89，λ（em）455 nm）的非常强的蓝色发光荧光团的创建，以及NMe（2）组（Phi（f）= 0.999，log epsilon 4.75，lambda（em）555 nm）。还发现6和7的Phi（f）溶剂依赖性相反，并且在整个sigma（p）-X区域中，Phi（f）和sigma（p）-X之间存在线性关系。
• Can Polarization of Triple Bond in Tolanes Be Deduced from ¹³C NMR Shifts? Re-evaluation of Factors Affecting Regiochemistry of the Palladium-Catalyzed Hydrostannation of Alkynes
  作者：Michael Rubin、Alexander Trofimov、Vladimir Gevorgyan

  DOI：10.1021/ja051274v

  日期：2005.7.1

  Polarization of the triple bond in a series of differently substituted ortho- and para-tolanes has been studied by NMR and computational methods in order to examine if C-13 NMR data can be effectively used for the assessment of electronic polarization of a triple bond in diarylacetylenes. DFT calculations of both natural charges and NMR properties revealed that chemical shifts concur with effective charges on sp-carbon atoms in para-tolanes, whereas in ortho-analogues magnetic anisotropy complicates the analysis making C-13 NMR data inapplicable for ascribing triple bond polarization. The obtained information was used to reevaluate factors affecting the regiochemistry of the Pd-catalyzed hydrostannation of the triple bond in tolanes. Computational study on the polarization of triple bonds taken together with the experimental data on hydrostannation of various mono- and disubstituted tolanes bearing para- and ortho-substituents demonstrated that the regioselectivity of hydrostannation is governed by a combination of electronic and steric factors. In para-tolanes, the electronic effect prevails and alpha- and beta-vinylstannanes are obtained predominantly for substrates with electron-withdrawing and electron-donating groups, respectively. In the ortho-series, steric factors dominate over electronics and a-isomers are produced with high selectivity regardless of the substituents' nature. However, it was found that in disubstituted "push-pull" tolanes steric control of an ortho-group can be overruled by the very strong electronic effect of an electron-withdrawing substituent in para-position.